Process for breaking petroleum emulsions



Patented Mar. 2%, i944 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University Keiser. Webster Groves, Mm,

City, and Bernhard I aasignors to Petrolite Corporation, Ltd Wilmington, Deb, a corporation of Delaware No Drawing. Application May 25, 1942, Serial No. 444,465

9 Claims.

This invention relates primarily to the resolution of petroleum emulsions.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil," emulsified oil, etc., and which comprise fine droplets of ham-- rally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from: mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned, is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The compounds used as the demulsifying agent or our process, are obtained by sulphation of the oxyalkylation products derived by the oxyalkylation of compounds sometimes referred to as acidyl-aryl-sulphonimids". (See U. S. Patent No. 1,145,499, dated July 15, 1915, to Biickel.)

Such sulphonimids represent the product ob- I tained by the introduction of two acyl radicals into the ammonium radical, one acyl radical be-, ing derived from a high molal detergent-forming monocarboxy acid, and the other acyl radical being derived from an aryl sulfonic acid.' Since the word acyl can properly be employed to describe both such acidic radicals, it is convenient to use the word acidyl in a limited sense to refer to the acyl radical derived from a carboxy acid.

The expression detergent-forming monocarboxy acds has been frequently employed in the literature to designate certain high molal acids having at least 8 and not more than 32 carbon atoms, and characterized bythe fact that they combine with alkali to form soap or soap-like materials. The commonest examples are higher fatty acids derived from animal, vegetable, or marine sources. Other well-known .examples include resinic acids, such as abietic acid, naturally-occurring petroleum acids such as those obtained by the oxidation of' petroleum hydrocarbons, waxes and the like. and fromcertain naturally-occurringwaxes. Such mpnocarboxy detergent forming acids may be cyclic or acyclic. They may be saturated or unsaturated. Included also are derivatives which do not eliminate the soap-forming property and which are obviiously chemical equivalents of the unmodified terial prior to cyclic. In the polycyclic type (on. 252-336) g Y acid. For instance, chlorinated olelc acid will serve as satisfactorily as oleic acid. Hydrogenated abietic acid is as satisfactory as the mahydrogenation. Brominated naphthentic acid is as satisfactory as the naphthenic acid itself. This alsoapplies to similar derivatives obtainable from oxidized petroleum acids, wax acids, etc. v

The aryl group may be monocyclic or polythe rings may-be One or more alkyl radicals maybe substituted in aromatic'nucleus, fgr instance, derivatives may be obtained from toluene, xylene, cymene, methylnaphthalene, diisopropylnaphthalene, amylated naphthalene, and similar aromatics, in which the alkyl side chain may contain as many as twenty carbon atoms. Other unfunctional present. The usual procedure is to react the se-. lected aromatic compound with chlorosulfonic acid, or use any other suitable reactant to obtain the sulphonchloride. The sulphonchloride is then reacted with ammonia to yield the sulphonamid. As to a more complete list of suitable aromatic compounds, see U. 8. Patent No. 2,248,- 342, dated July 8, 1941, to De Groote and Wirtel. This patent includes, among others, aromatic compounds obtained by introducing the octadecyl radical into the aromatic nucleus. Such radical can be introduced into benzene, naphthalene, diphenyl into a substituted benzene, a

separated or fused.

substituted naphthalene, or a substituted diphonchlorides depends upon reacting the-corresponding sulfonic acid with certain non-metallic halid such as sulphurchlorides, or phosphorous chlorides or the like. One can prepare numerous substituted aromatic sulfonic acids in the manner described in U. S. Patent No. 2,278,167, dated March 31, 1942, to De Groote and Keiser. It is, of course, understood that unsubstituted aromatic sulfonic acids may be employed, and in fact, in some instances are available as inexpensive by-products. The manufacture of the acyl chlorides presents no particular difliculty, especially when manufactured from high moial saturated monocarboxy acids. Reference is made to the manufacture from saturated fatty acids, from naphthenic tained from naturally-occurring waxes, oxidized petroleum acids, etc. Some of the procedures employed for preparing the high molal acyl chlorides are not as satisfactory when unsaturated acids such as -oleic acids are employed. Thus,

substituents may also be acids, wax acids ob-- cthylenic acids. The same is quired.

sulphur chloride may serve satisfactorily for preparing the acyl chloride from stearic acid, but is not as satisfactory, if oleic acid is used. Phosphorous chlorides, for instance, phosphorous pentachloride, may be used equally satisfactorily,

as a rule, with either saturated acids, or monotrue of thionyl chloride. As to such procedures, see aforementioned Biickel patent. When the high molal acids are of the polyethylenic type, or contain some other functional group, in addition to. a single ethylene linkage, other difliculties may be encountered and special methods may be re- When a sulphonamid; particularly a monocylic sulphonamid free from nuclear substituted alkyl radicals, or having, at the most, short chain alkyl radicals present, is treated with suitable acidyl chloride, 'one obtains practically a quantitative yield of the acldyl-arylsulphonimid. This procedure is so simple that it may be readil illustrated by the procedure described in the aforementioned Biickel patent. The short alkyl chain or chains preferably have less than 6 carbon atoms.

ACIDYL-ARYL-SULPHONIMID Example I 98 kilos of sodium benzenesulfonamid are heated in an oil bath for about 1-2 hours at about 100-120" 0., with 152 kilos of stearic acid chloride. When recrystallized ifrom alcohol, the crude product melts at 104 C.

AcrnYL-AnYL-Smrnommm Example 2 in which R1, R2, or alkyl radicals containing one to twenty carbonatoms. R is an aromatic nucleus of the monocyclic or pol cyclic type, and R'is an acidyl radical obtained from a high molal detergentforming monocarboxy acid having at least 8 carbon atoms and not more than 32 carbon atoms.

We have found that if an acidyl-aryl-sulphonimid of the kind above described is treated with an oxyalkylating agent in the customary manner employed to oxyalkylate a phenol, a high molal acid, or the like, one obtains a variety of valuable intermediates which may be water-insoluble, or water-miscible, or water-soluble, depending upon the nature of the oxyalkylating agent used, and the molar proportion of oxyalkylating agent to sulphonimid. The presence 01' the two acyl radicals, one of which is a sulfonyl radical, in the sulphonimid molecule, makes the imid acidic.. Such compounds combine with alkalies to give salts. Compare with the wellknown Hinsberg reaction. Thus, essentially, the same procedure may be employed in oxyalkylation as is used in the treatment of high molal and R3 represent hydrogen atoms I suli'onic acids. No. 2,208,581, dated July 23, 1940, to Hoeflfelman. Briefly stated, the procedure employed is to treat the anhydrous sulphonimid with a suitable alkylating' agent containing a reactive ethylene ox ide ring. As typical examples of applicable compounds may be mentioned glycerine epichlorhydrin, glycide alcohol, ethylene oxide, propylene oxide, butene-2-oxide, butene-l-oxide, isobutylene oxide, butadien oxide, butadiene dioxide, chloroprene oxide, isoprene oxide, decene oxide, styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc. The reactive olefine oxide which we prefer to employ is propylene oxide, butylene oxide, glycidol. and methyl F-gIycidoI, and especially ethylene oxide. 4

As intermediates for subsequent sulfation we particularly prefer the type of oxyalkylated product in which a comparatively small amount of olefine oxide is used per mole of acidyl-aryl-sulphonimid. Indeed, reaction in molar proportions, 1. e., one mole of the clefine oxide, per mole of imid supplies a suitable intermediate sequent sulfation, insofar that such minimum oxyalkylation is sufiicient to introduce an alcoholic radical. Our preference, then, is to sulfate the water-insoluble. oxyalkylation products. However, one may sulfate the water-miscible oxyalkylation products, and for that matter, one may even sulfate the oxyalkylation products which are already water-soluble. .Peculiarly enough, in the latter case, such products sometimes exhibit increased eflfectiveness asdemulsifiers and also as emulsifiers.

In a general way, the larger the proportion of oxyalkylating agent per mole of sulphonimid, the greater the hydrotropic and hydrophile proportions. Thus, 5 to 10 moles of ethylene oxide per mole of sulphonimid greatly enhances such properties. If 20 to 60 moles of the oxyalkylating agent, particularly ethylene oxide, is employed,

one obtains an intermediate of pronounced watersolubility, provided that the molal weight of the initial sulphonimid is not too large. Generally speaking, a of two moles of ethylene oxide must be introduced for each carbon atom in the sulphonimid to insure complete watersolubility in the intermediate product, prior to sulfation.

.Considering momentarily intermediate products derived fromethylene oxide, they may be depicted in the following manner:

in which all the characters have their previous significance and n may represent any number from 1 to 60.

In view of what has been said, it hardly appears .necessary to include examples of the intermediate product beyond stating that oxyalkylation can generally be conducted under mild conditions of reaction. For instance, a temperature of loo- C. is usually satifactory; secondly, pressure of less than 200 lbs. per sq. in. gauge pressure is usually satifactory, the reaction may take place in a comparatively short period, for instance, two hours or less, but in other instances as long as twenty hours may be employed. The reaction is conducted by using a suitable apparatus that insures intimate contact between the oxyalkylating agentand the'sulphonimid. After the introduction of the first molecule of ethylene oxide or oxyalkylating agent, acidity has disap- For instance, see U. s. Patent for sub-' glycidol.

peared, and the subsequent stages are sometimes suitably catalyzed by the presence of a small amount of alkali, such as caustic'soda, sodium methylate, soap,

or the like, which may be present to the extent of one tenth of 1% to one-half of 1%. Compare with the oxyalkylation of high molal alcohols.

OXYALKYLATED ACIDYL-ARYL-SULPHONIMID Example 1 Stearyl benzene sulphonimid sodium salt is dissolved in any suitable solvent, such as benzene or alcohol, and treated with dry hydrochloric acid gas so as to liberate the imid with the prepound moles of ethylene oxide for each pound mole of the substituted imid.

OXYALKYLATED ACmYt-ARYL-SULPHoNIMm Example 3 The same procedure is followed as in the preceding example, except that 10-20 pound moles of ethylene oxide are used for each pound mole of the substituted imid.

OXYALKYLATED ACIDYL-ARYL-SULPHONIMID Example 4 Palmityl paratoluene sulphonimid obtained in I the manner previously described, is substituted for stearyl benzene sulphonimid in Examples 1-3 preceding.

OXYALKYLATED ACIDYL-ARYL-SULPHONIMID Example 5 The same procedure is followed as in Examples 1-3 preceding, except that the sulphonimid is derived from mixed high molal fatty acid chlorides of the kind available in the open market, and the sulphonimid is derived from cymene.

As has been suggested, one need not employ the sulphonimid derived from a single fatty acid,

but one may employ theimid derived from a mixture of fatty acids, and especially, from the mixture obtained by the hydrogenation of naturally-occurring fats or oils. For instance, unsaturated naturally-occurring oils, such as olive oil, teaseed' oil, soyabean oil, cottonseed oil, etc. may be hydrogenated and then subjected to saponification or hydrolysis. The mixture of fatty acids so obtained or the mixture obtained from palm oil, or palm kernel oil, may be converted into a corresponding acyl chloride and employed in the present instance. Attention is again directed to the fact that it is our preference to use an oxyalkylating agent having not over 4 carbon atoms, i. e., ethylene oxide, propylene oxide, butylene oxide, glycidol, and methyl Having obtained anpoxyalkylation product of the kind described, i. e., an acidyl-aryl-sulphonimid into which a hydroxyalkyl group has been introduced, or the equivalent, i. e., one in which the carbon atom chain of the alkyl group-has been interrupted at least 'once' by oxygen, one

by means of strong sulfonating agents, previously need only proceed to sulfate or sulfonate such alcoholic body. If it happens that the acidyl group contains an unsaturated linkage, for instance, derived from a monoethylenic acid, such as oleic acid, then in that event, sulfation or sulfonation might take place to a limited degree at such particular functional group. Also it is possible to produce a true sulfonic acid by conditions of sulfonation which either introduces a sulfonic group into the aromatic nucleus, or even by substitution into the acidyl group. Such last named reaction is not apt to take place except under conditions that are apt to cause decomposition. Introduction of a'sulfonic radical into an aromatic nucleus, particularly if a polycyclic aromatic compound is employed, may result in the production of a particularly valuable compound, being one characterized by the presence of both the organic sulfate radical and also the organic sulfonated radical. At this point it is desired to emphasize the previous reference that has been made to the fact that any non-functional substituent may be present in the aromatic nucleus, but such statement is qualified at this point so as to include the sulfonic acid radical, with the full understanding that such radical is functional. Generally speaking. one is more apt to obtain sulfonic acid radicals in the organic nucleus, if strong sulfonating agents are used. Subsequent reference is made to this same terminology.

Returning, then, to the sulfation process per se, it is to be remembered that it is commonly referred to as a sulfonation process, even though no true sulfonic acid is necessarily formed to any significant amount. Compare, for example, with the sulfonation of castor oil, red oil, or the like. On the other hand, in the present instance, true sulfonic acids may or may not be formed. Thus, the term sulfonating agent is used synonymously with sulfation agents. One may use any ofthe general procedures employed for sulfating or sulfonating fats, fatty acids, alcohols, aromatic materials, and the like. Generally speaking, sulfuric acid of at least 66, or stronger, is employed. Sometimes 100% sulfuric acid is employed. Not infrequently sulfation or sulfonation is conducted referred to. By the expression strong sulfonating agents is meant sulfonating agents of greater sulfonating'power than 100% sulfuric acid. Included, among such sulfonating agents are compounds which per se have a greater sulfonating power than 100% sulfuric acid, such as, for example, sulfur. trioxide, chlorsulfonic acid, bromosulfonic acid, oleum and acetyl sulfuric acid. In practice, it is preferable to employ this class of sulfonating agents, and especially desirable results have been obtained with chlorsulfonic acid. Where sulfur trioxide is employed, it may be introduced into the reaction mixture either in gaseous, liquid or solid form. As examples of other strong sulfonating agents may be mentioned milder sulfonating agents, such as sulfuric acid, in combination with reagents capable of removing water from the reaction mass, such as, for example, acetyl chloride, glacial acetic acid, acetic anhydride, propionic acid, propionic anhydride, phosphorous pentoxide, phosphorous oxychloride, and boric anhydride. If desired, dehydrating agents may be employed in connection with the sulfonating agentswhich in themselvesare strongly sulfonating, viz., sulfur trioxide, chlorsulfonie acid, oleum and the like,

the sulfonation may vary instance, with caustic but there appears to be very little added advantage in such a procedure.

The proportions of the sulfonating agents may vary within relatively wide limits, depending largely upon. the nature of the reactants. In

general, it.is preferable to employ about 1 to 2- moles of sulfonating agent per mole of the. hy-

droxylated reactant. In certain cases, however, it may be desirable to use larger or smaller proportions of the sulfonating agent, it being understood that the desired reaction proceeds whether a small or large amount of sulfonating agent is employed.

The sulfonation may be effected in a solvent or suspension medium, that is to say, a medium which is liquid at the temperature of the reaction and is inert to the reactants or does not reaction unfavorably. As examples of solvent or suspension media, one may mention carbon tetrachloride, ethylene dichloride, trichlorethylene, tetrachlorethane, chloroform, liquid sulfur dioxide, diethylether, acetic anhydride, propionic acid and propionic anhydride. Generally speaking, it

is preferable to employ carbon tetrachloride. Solvent or suspension media are especially desirable when the sulfonating agent is sulfur trioxide.

The time allowed for the sulfonation to take place will depend largely upon the nature of the reactants and the conditions of temperature. Under ordinary operating-conditions it may vary from about 2 to 48 hours. If desired, the sulfonation may be carried on almost indefinitely. In practice, therefore, it is customary to carry out this reaction until further sulfonation has little if any eifect on the results obtained.

While the temperature maintained'in eifecting within relatively wide limits, the temperature employed should preferably be below that giving rise to decomposition, resinification, or polymerization of the reactants and products. In general, it is preferable to maintain the temperatures in this step of the process below about 50 C.,- and preferably, within the range of aboutto +30 C. Ordinarily, higher temperatures tend to yield darker products, and also to cause the liberation of sulfurdioxide. The sulfonated mass is washed in the usual manner. The purpose of such step is to stop the reaction and separate the excess sulfonating agent from the sulfonated product. The conventional procedure includes the use of water, salt solution, sulfate solution, or even cracked ice. Generally speaking, the wash water is added in bulk, and under such conditions that the temperature rise which takes place does not exceed the maximum temperature of sulfonation. Such operating steps generally prevent excessive drolysis. Sometimes hydrolysis is desired. Especiallyif a .sulfonic group has been introduced, and it is desired to eliminate the sulfate group. As to conditions encouraging hydrolysis follow ing sulfonation, see U. S. Patent No. 2,083,222, dated-June 8, 1937, to Melvin De Groote. As to conventional procedure involving the sulfonation of aromatic materials generally, see aforementioned U. 8. Patent N 2,278,167, dated March 31, 1942, to De Groote and Wirtel. As the general procedure for preparing Turkey red oils and the like by sulfonation is so well known that further description is not required.

After the washing step is complete and the waste acid water withdrawn, the residual .mass may be neutralized in any suitable manner, for

soda, caustic potash, am-

aifect the monia, monoethanolamine, diethanolamine, triethanolamine, amylamine, cyclohexylamine, benzylamine, tris (hydroxymethyDaminomethane, ethylenediamine, diethylene-triamine, etc. If desired, one may replace the acidic hydrogen atom by a metal, such as calcium, magnesium, iron, copper, etc.

preceding description, but for the sake of convenience, the following is included:

SULroNArsn OXYALKYLA'IED ACIDYL-ARYL-SUL- rnommn Example 1 One pound mole of an. oxyalkylated acidylaryl-sulphonimid of the kind exemplified by Example l, preceding, is treated with one to two 'usual manner, and the waste acidwithdrawn.

The sulfonated mass is neutralized with ammonia until distinctly alkaline to methyl orange indicator.

Surromrno OXYALKYLATED ACIDYL-ARYL-SUL- rnomsmi Ezamplez The same procedure is employed as in Example 1, preceding, except-that oxyalkylated acidyl-arylsulphonimid 0f the kind exemplified by Examples 2 to 5, preceding, are employed, instead of the sulphonimid exemplified by Example 1.

SULFONATED OXYALKYLATED ACIDYL -ARYL-SUL- PHONIMID Example 3 The same procedure is employed as in Example 2, preceding, except that the sulphonimid is one in which the aromatic nucleus is a naphthalene ring.

Sunromrsn OXYALKYLATED ACIDYL-ARYL-SUL- rnormno Example 4 SULFONATED OXYALKYLATED ACIDY L-ARYL-SUL- PHONIMID Example 5 The same procedure is followed as in Examples 3 and 4, preceding, except that sulfuric acid 18 lubstituted for 66 acid.

SULI'ONATED Oxnrxmrrn ACIDYL-ARYL-SUL- rnomum Example 6 The same procedure is followed as in Examples 3 and 4, preceding, except that oleum of approximately 25% strength is employed instead of 66 sulfuric acid.

In view of what has been said. it is obvious that types of compounds herein one of the principal contemplatcd'can be characterized by the follow- It is not believed that a specific example is required, in view of the elaborate "lug formula, in which all of the characters have their previous significance:

' gasoline, kerosene,

wherein Z is a cation. Such formula, however, does not depict the herein contemplated new composition of matter or demulsifier in its broadest aspect, for the same reason that the composition of a Turkey red oil cannot be depicted by the formula showing the structure of a sulforicinoleic acid. Previously it has been pointed out that hydrolysis does take place, to a greater or lesser degree, during the washing process, and that a true sulfonic group might be introduced into R. For this reason the only satisfactory description of the invention in its broadest aspect must reside in the reference to the method of manufacture. Products of the kind described above, of course could be separated in comparatively pure form, by conventional procedure, involving, for example, extraction of the neutral aqueous solution with benzene, so as to eliminate unsulfonated material.

For practically all purposes, a sulfonation product as prepared following previous descriptions and without separating or purification, is entirely satisfactory.

Conventional demulsifyi'ng agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as stove oil, a coal tar product, such as benzene, cresol, anthracene oil, etc.

toluene, xylene, tar acidoil, Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl are concerned; but we have found that such a demulsiiying agent has commercial value, as it will economically break or resolve oil field emu'lcases which cannot be low a cost with the desions in a number of treated as easily or at so mulsiiying agents heretofore available.

In practising our process, a treating agent or demuisifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process.

Having thus described our invention, what we claim as new and desire to secure by Letters Patcut is:

l. A process for breaking petroluem emulsions of the water-in-oil type, characterized by subjectalcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as ine oil, carbon tetrachloride, sulfur dioxide-extract obtained'in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials herein described, may be admixed with one customarily used in connection with conventional demulsiiying agents. Moreover, said material or materials may, be used alone, or in admixture with other suitable well-known classes of demulsifying agents.

It is well-known that conventional demulsifying agents may be used in awater-soluble form; or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration em- .ployed. This same fact is true in regard to the material or materials herein described.

We desire to point out that the superiority of the reagent or demulsifying agent employed in our herein described process for breaking petroleum emulsions, is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available-demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will findcomparatively limited application, so far as the majority of oil field emulsions or more of the solvents I ing the emulsion to the action of a demulsifying agent comprising a. sulionated oxyalkylated rerivative oi an acidyl-aryl-sulphonimid of the formula:

in which R. acidyl radical obtained from a high molal detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 32; carbon atoms; said derivative being obtained by means of an oxyalkylating agent having. a reactive ethylene oxide ring.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of ademulsiiying agent comprising a sulionated oxyalkylated derivative of an acidyl-aryl-sulphonimid of the formula:

II R.SO:.N/

R in which R is .an aromatic nucleus, and R is an acldyl radical obtained from a high molal detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 32 canbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ethylene oxide ring; said oxyalkylating agent having not more than 4 carbon atoms.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion tying agent comprising a sulfonated oxyalkylated derivative of an acidy -aryl-sulphonimid of the formula:

nsom

in which R is an aromatic nucleus having at least 1 alkyl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from a high molal detergent-forming monocarboxy acid having at least 8 carbon atoms and not more than 32 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ethylene oxide ring; said oxyalkylating agent having not more than 4 carbon atoms.

is an aromatic nucleus, and R is an to the action of a demulsisaid oxyalkylating carbon atoms.

4. A process for breaking petroleum emulsions of the water-in -oil type, characterized by sub- J'ecting the emulsion to the action of a demulsifying agent comprising a sulfonated oxyalkylated derivative of an acidyl-aryl-sulphonimid of the.

formula:

in which R is a monocyclic aromatic nucleus hav-v ing at least 1 alkyl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from a high molal detergent-forming monocarb'oxy acid having at least 8 carbon atoms and not more than 32 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ethylene oxide ring: agent having not more than 4 carbon atoms.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a sulfonated oxyalkylated derivative of an acidyl-aryl -sulphonimid of the formula:

H Rsom in which R is a monocyclic aromatic nucleus having at least 1 alkyl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from a. higher fatty acid having at least 8 and not more than 32 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ethylene oxide ring: 7

said oxyalkylating agent having not more than 4 6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a sulfonated oxyalkyla'ted derivative of anacidyl-aryl-sulphonimid of they formula:.

R.SO:.N/

. I in which R is a monocyclic aromatic nucleus having at least 1 alkyl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from an unsaturated higher fatty acid having at least 8 and not more than 32 carbon atoms; said derivative being obtained by means of an oxyalkylating agent having a reactive ething not more than 6 carbon ato ring: said onalblating agent havthan 4 carbon atoms.

7. A process for breaking. petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a sulfonated oxyethylated derivative of an acidyl-aryl-sulp'honimid of the formula: a

ylene oxide in which R is a monocyclic aromatic nucleus having at least one'alkyl side chain containing less than 6 carbon atoms, and R is an acidyl radical obtained from an unsaturated higher fatty acid having at least 8 and not more than 32 carbon atoms; said onethylated derivative being of the water-miscible type.

9. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the ing agent comprising a sulfonated oxyethylated derivative of an acidyl-aryl-sulphonimid of the formula:

R! in which R is a monocyclic aromatic nucleus having at least one alkyl side chain containing less and R is an acidyl radical obtained from an unsaturated higher fatty acid having at least 8 and not more than 32-carbon atoms: said oxyethylated derivative being of the water-soluble'type. v

MELVIN DE GROO'I'E. BERNHARD KEISER action of a demulsify- 

